CN109096434A - A kind of triazole type molecular blotting polymer microsphere and its preparation method and application - Google Patents
A kind of triazole type molecular blotting polymer microsphere and its preparation method and application Download PDFInfo
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- CN109096434A CN109096434A CN201810890894.4A CN201810890894A CN109096434A CN 109096434 A CN109096434 A CN 109096434A CN 201810890894 A CN201810890894 A CN 201810890894A CN 109096434 A CN109096434 A CN 109096434A
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- 150000003852 triazoles Chemical class 0.000 title claims abstract description 67
- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 239000004005 microsphere Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 238000001338 self-assembly Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- -1 acrylic ester Chemical class 0.000 claims abstract description 16
- 238000010828 elution Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000004088 foaming agent Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000002604 ultrasonography Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 17
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 claims description 17
- 239000003899 bactericide agent Substances 0.000 claims description 16
- 238000001514 detection method Methods 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000002825 nitriles Chemical class 0.000 claims description 7
- 241000894006 Bacteria Species 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 150000003851 azoles Chemical class 0.000 claims description 6
- FQKUGOMFVDPBIZ-UHFFFAOYSA-N flusilazole Chemical compound C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 FQKUGOMFVDPBIZ-UHFFFAOYSA-N 0.000 claims description 6
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 5
- STMIIPIFODONDC-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)hexan-2-ol Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(O)(CCCC)CN1C=NC=N1 STMIIPIFODONDC-UHFFFAOYSA-N 0.000 claims description 5
- 239000005822 Propiconazole Substances 0.000 claims description 5
- 239000005839 Tebuconazole Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 claims description 5
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 3
- ZESXUEKAXSBANL-UHFFFAOYSA-N trifluoromethyl prop-2-enoate Chemical compound FC(F)(F)OC(=O)C=C ZESXUEKAXSBANL-UHFFFAOYSA-N 0.000 claims description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 229920000344 molecularly imprinted polymer Polymers 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 13
- 125000002133 (4-hydroxy-3-iodo-5-nitrophenyl)acetyl group Chemical group OC1=C(C=C(C=C1I)CC(=O)*)[N+](=O)[O-] 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical group FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 7
- 241000208125 Nicotiana Species 0.000 description 7
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 7
- 230000009102 absorption Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010811 Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
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Abstract
The present invention provides a kind of preparation methods of triazole type molecular blotting polymer microsphere, belong to molecularly imprinted polymer technical field, the following steps are included: carrying out self assembly after ultrasound under oxygen-free environment after triazole class compounds template molecule, function monomer and pore-foaming agent are mixed, prepolymerization is carried out after self assembly mixed liquor is mixed with acrylic ester cross-linking agent, azo-initiator, polymerization reaction will be carried out under the conditions of earthquake after the heating of obtained prepolymerization liquid, obtains polymer；By the triazole class compounds template molecule elution in obtained polymer, triazole type molecular blotting polymer microsphere is obtained.Molecular blotting polymer microsphere particle size distribution prepared by the present invention is single, and has good specific adsorption ability to template molecule and its analogue.
Description
Technical field
The present invention relates to molecularly imprinted polymer technical field, in particular to a kind of triazole type molecular blotting polymer microsphere
And preparation method thereof.
Background technique
Triazole bactericidal agent refers to the compound containing 1,2,4- triazole ring, and due to having, less toxic, absorbability is strong, the lasting period
The advantages that long, is widely used in the prevention and treatment of the pest and disease damages such as water fruits and vegetables, paddy.Phillips McDougall was to 2015
The important preceding 15 fungicide sales volumes in the whole world are counted, wherein including 5 kinds of triazole bactericidal agents, it is seen that it is importantly
Position.But with the extensive use of triazole pesticide, residue problem in agricultural product and environment also gradually causes the weight of people
Depending on.
Molecular imprinting technology, which refers to, prepares a kind of macromolecule for capableing of specific recognition target molecule and its analogue
The technology of synthetic material, in recent years, this technology have obtained certain in the analysis of triazole bactericidal agent pesticide trace residue
Research and application.Xu Yongxin etc. has invented a kind of triazole pesticide molecular blotting polymer microsphere solid-phase extraction column and its application
Method, using triazolone as template molecule, methacrylic acid be function monomer, trimethylol-propane trimethacrylate is crosslinking
Agent, azodiisobutyronitrile are to remove template molecule after initiator reacts in atent solvent, obtain point with certain adsorptivity
Sub- imprinted polymer microballoon.But the polymer partial size of this method preparation is larger, at 2 μm or so, specific adsorption effect is poor.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of triazole type molecular blotting polymer microsphere and preparation method thereof,
Triazole type molecular blotting polymer microsphere granularity provided by the invention is small, and particle diameter distribution is single, and specific adsorption effect is good.
The present invention provides a kind of preparation methods of triazole type molecular blotting polymer microsphere, comprising the following steps:
1) it is carried out after ultrasound under oxygen-free environment after mixing triazole class compounds template molecule, function monomer and pore-foaming agent
Self assembly obtains self assembly mixed liquor；
2) it is carried out after mixing the self assembly mixed liquor that step 1) obtains with acrylic ester cross-linking agent, azo-initiator
Prepolymerization obtains prepolymerization liquid；The prepolymerized temperature is 20~40 DEG C；
3) polymerization reaction is carried out after the prepolymerization liquid that step 2) obtains heating up, obtains polymer；The heating
Rate is 0.5~1.2 DEG C/min, and the polymerization temperature is 35~60 DEG C；
4) the triazole class compounds template molecule elution in the polymer for obtaining step 3) obtains triazole type molecular engram
Polymer microballoon；
It is carried out under the conditions of the polymerization reaction earthquake in prepolymerization and the step 3) in the step 1).
Preferably, in the step 1) triazole class compounds template molecule be triazolone, nitrile bacterium azoles, Tebuconazole, hexaconazole,
Olefin conversion, propiconazole, tricyclazole, glyoxalin or Flusilazole.
Preferably, function monomer is acrylic acid, α-methacrylic acid, trifluoromethyl acrylate or propylene in the step 1)
Amide.
Preferably, pore-foaming agent is chloroform, toluene, acetonitrile or methylene chloride in the step 1).
Preferably, the amount ratio of triazole class compounds template molecule, function monomer and pore-foaming agent is in the step 1)
1mol:2~6mol:30~60ml.
Preferably, the temperature of self assembly is 4~30 DEG C in the step 1), and the time of the self assembly is 2~12h.
Preferably, acrylic ester cross-linking agent is ethylene glycol dimethacrylate or trihydroxy methyl third in the step 2)
Alkane trimethyl acrylic ester.
Preferably, azo-initiator is azodiisobutyronitrile or azobisisoheptonitrile in the step 2).
Preferably, acrylic ester cross-linking agent, azo-initiator and triazole class compounds template point in the step 2)
The mass ratio of son is 4~20:1:1.
Preferably, the concussion condition is provided by constant temperature oscillator, and the revolving speed of the isothermal vibration device is 50~150rpm.
The present invention also provides the triazole bactericidal agent molecular blotting polymer microsphere that above-mentioned preparation method is prepared, institutes
State polymer microballoon granularity be 190~220nm, the size distribution of the polymer microballoon is single, average particle size be 198nm~
203nm。
The present invention also provides application of the above-mentioned polymer microballoon in the residual trace detection of triazole bactericidal agent agriculture.
Advantageous effects: the present invention causes precipitation polymerization process using heat, by self assembly, prepolymerization, polymerization process
Triazole type molecular blotting polymer microsphere is prepared.Molecular blotting polymer microsphere grain diameter prepared by the present invention is small, grain
Diameter distribution is single, and has good specific adsorption ability to triazole type template molecule and its analogue.Implement number of cases
According to show triazole type molecular blotting polymer microsphere average grain diameter provided by the invention be 198nm~203nm.
2.4 are not less than to triazole type template molecule imprinting factor.
Detailed description of the invention:
Fig. 1 is the electron-microscope scanning figure of MIPs obtained in embodiment 1；
Fig. 2 is the particle size distribution figure of MIPs obtained in embodiment 1；
Fig. 3 is the Static Adsorption curve of MIPs obtained in embodiment 1；
Fig. 4 is spy of the MIPs and NIPs obtained in embodiment 1 to 9 kinds of triazole bactericidal agents and 2 kinds of non-triazole pesticides
Opposite sex absorption figure；
Fig. 5 is the particle size distribution figure of MIPs obtained in embodiment 3；
Fig. 6 is the particle size distribution figure of MIPs obtained in embodiment 4.
Specific embodiment
The present invention provides a kind of preparation methods of triazole type molecular blotting polymer microsphere, comprising the following steps:
1) it is carried out after ultrasound under oxygen-free environment after mixing triazole class compounds template molecule, function monomer and pore-foaming agent
Self assembly obtains self assembly mixed liquor；
2) it is carried out after mixing the self assembly mixed liquor that step 1) obtains with acrylic ester cross-linking agent, azo-initiator
Prepolymerization obtains prepolymerization liquid；The prepolymerized temperature is 20~40 DEG C；
3) polymerization reaction is carried out after the prepolymerization liquid that step 2) obtains heating up, obtains polymer；The heating
Rate is 0.5~1.2 DEG C/min, and the polymerization temperature is 35~60 DEG C；
4) the triazole class compounds template molecule elution in the polymer for obtaining step 3) obtains triazole type molecular engram
Polymer microballoon；
It is carried out under the conditions of polymerization reaction earthquake in prepolymerization and step 3) in the step 2).
The present invention by triazole class compounds template molecule, function monomer and pore-foaming agent mix after after ultrasound under oxygen-free environment
Self assembly is carried out, self assembly mixed liquor is obtained.
In the present invention, the triazole class compounds template molecule be preferably triazolone, nitrile bacterium azoles, Tebuconazole, hexaconazole,
Olefin conversion, propiconazole, tricyclazole, glyoxalin or Flusilazole.
In the present invention, the function monomer is preferably acrylic acid, α-methacrylic acid, trifluoromethyl acrylate or propylene
Amide.
In the present invention, the pore-foaming agent is preferably chloroform, toluene, acetonitrile or methylene chloride.
In the present invention, the amount ratio of the triazole class compounds template molecule, function monomer and pore-foaming agent is preferably
1mol:2~6mol:30~60ml, more preferably 1mol:3~5mol:45~55ml.
In the present invention, the frequency of the ultrasound is preferably 20~40kHz, more preferably 25~30kHz；The ultrasound
Time is preferably 10~20min, more preferably 15min；The temperature of the ultrasound is preferably 20~30 DEG C, and more preferably 25 DEG C.
The present invention is preferably passed through nitrogen in ultrasonic procedure and provides oxygen-free environment.
In the present invention, the temperature of the self assembly is preferably 4~30 DEG C, more preferably 10~25 DEG C, most preferably 15
~20 DEG C；The time of the self assembly is preferably 2~12h, more preferably 5~10h.
In the present invention, the template molecule and function monomer mainly pass through hydrogen bond action；Pore-foaming agent is solvent, to hydrogen bond
Formation have a certain impact.
The sequence and method that the present invention mixes triazole class compounds template molecule, function monomer and pore-foaming agent be not special
It limits, selects sequence and method well known to those skilled in the art.
After obtaining self assembly mixed liquor, the present invention is by obtained self assembly mixed liquor and acrylic ester cross-linking agent, azo
Prepolymerization is carried out after the mixing of class initiator, obtains prepolymerization liquid；The prepolymerized temperature is 20~40 DEG C.
In the present invention, the acrylic ester cross-linking agent is preferably ethylene glycol dimethacrylate or trihydroxy methyl third
Alkane trimethyl acrylic ester.
In the present invention, the azo-initiator is preferably azodiisobutyronitrile or azobisisoheptonitrile.
In the present invention, the acrylic ester cross-linking agent, azo-initiator and triazole class compounds template molecule
The mass ratio of the material is preferably 4~20:1:1, more preferably 10~15:1:1.
In the present invention, the prepolymerized temperature is preferably 25~35 DEG C, and more preferably 30 DEG C；When described prepolymerized
Between preferably 2~4h, more preferably 3h.
In the present invention, it is carried out under the conditions of the preferred earthquake of the prepolymerization.
In the present invention, the condition of swinging preferably is provided by constant temperature oscillator, and the revolving speed of the isothermal vibration device is preferably
50~150rpm, more preferably 80~120rpm, most preferably 100~110rpm.
The sequence and method that the present invention mixes self assembly mixed liquor with acrylic ester cross-linking agent, azo-initiator do not have
There is particular determination, selects sequence and method well known to those skilled in the art.
After obtaining prepolymerization liquid, this hair carries out polymerization reaction after prepolymerization liquid heats up, and obtains polymer；Institute
The rate for stating heating is 0.5~1.2 DEG C/min, and the temperature of the polymerization reaction is 35~60 DEG C.
In the present invention, the heating rate is preferably 0.8~1.0 DEG C/min.The present invention is warming up to polymeric reaction temperature
Stop heating afterwards.
In the present invention, the temperature of the polymerization reaction is preferably 40~55 DEG C, and more preferably 45~50 DEG C；The polymerization
The time of reaction is preferably 16~for 24 hours, more preferably 18~22h, most preferably 20h.
In the present invention, it is carried out under the conditions of the preferred earthquake of the polymerization reaction.
In the present invention, the concussion condition is preferably provided by constant temperature oscillator, and the revolving speed of the isothermal vibration device is preferred
For 50~150rpm, more preferably 80~120rpm, most preferably 100~110rpm.
In the present invention, further preferably include standing to room temperature, centrifuge separation after the polymerization reaction, obtain polymer.
In the present invention, the centrifugal rotational speed of the centrifuge separation is preferably 10000~15000rpm, and more preferably 12000
~14000rpm；The time of the centrifugation is preferably 5~15min, more preferably 7~10min.
In the present invention, solid phase, solid phase drying to obtain polymer are obtained after the centrifugation.
The present invention is not particularly limited the dry method of solid phase, selects drying means well known to those skilled in the art i.e.
It can.
After obtaining polymer, the triazole class compounds template molecule elution in obtained polymer is obtained three by the present invention
Azole molecular blotting polymer microsphere.
The present invention is preferably dried polymer before elution.
In the present invention, the temperature of the drying is preferably 35~40 DEG C, and the time of the drying is preferably 2~3h.
In the present invention, the eluant, eluent of the elution is preferably the mixed solution of methanol and acetic acid.
In the present invention, the volume ratio of the methanol and acetic acid is preferably 2~10:1, more preferably 5~9:1.
In the present invention, the elution carries out preferably in Soxhlet extractor.
In the present invention, the number of the elution is preferably until can't detect template molecule in the supernatant after eluting.
In the present invention, further preferably successively include washing after the elution, dry, obtain triazole type molecularly imprinted polymer
Microballoon.
In the present invention, the detergent of the washing is preferably methanol.The present invention is not particularly limited the number of washing,
Washing to polymer is neutrality.
In the present invention, the temperature of the drying is preferably 30~50 DEG C, and more preferably 40~45 DEG C；The present invention is to drying
Time be not particularly limited, it is dry to constant weight.
In the present invention, the drying is preferably dried in vacuo.
The present invention also provides the triazole type molecular blotting polymer microsphere that above-mentioned preparation method is prepared, the polymerizations
The granularity of object microballoon is 190~220nm, and the size distribution of the polymer microballoon is single, average particle size 200nm.
The present invention also provides above-mentioned triazole type molecular blotting polymer microspheres in the residual trace detection of triazole bactericidal agent agriculture
In application.
In the present invention, it is preferred to successively carry out sample to be tested using triazole type molecular blotting polymer microsphere as adsorbent
Solid Phase Extraction and UPLC-MS/MS detection.
In the present invention, the triazole bactericidal agent be preferably triazolone, nitrile bacterium azoles, Tebuconazole, hexaconazole, olefin conversion,
Propiconazole, tricyclazole, glyoxalin or Flusilazole.
The present invention is not particularly limited the processing method of sample to be tested, selects method well known to those skilled in the art i.e.
It can.
In the present invention, triazole type molecular blotting polymer microsphere is preferably packed into solid-phase extraction column by the Solid Phase Extraction
In, it obtains carrying out Solid Phase Extraction by the solid-phase extraction column of adsorbent of triazole type molecular blotting polymer microsphere.
In the present invention, the mass volume ratio of the triazole type molecular blotting polymer microsphere and solid-phase extraction column is preferably
100mg:3mL.
In the present invention, the Solid Phase Extraction preferably successively includes pre-activate, activation, loading, elution and elution.
In the present invention, the preactivated pre-activate agent is preferably methanol.The present invention does not have the dosage of pre-activate agent
Particular determination selects dosage well known to those skilled in the art.
In the present invention, the activator of the activation is preferably acetonitrile.The present invention does not have special limit to the dosage of activator
It is fixed, select dosage well known to those skilled in the art.
In the present invention, the eluent of the elution is preferably the mixed liquor of first alcohol and water.The present invention does not have elution rate
There is particular determination, selects elution rate well known to those skilled in the art.
In the present invention, the volume ratio of the first alcohol and water is preferably 8:1, and the water is preferably ultrapure water.
In the present invention, the eluent is preferably the mixed liquor of methanol and acetic acid.
In the present invention, the volume ratio of the methanol and acetic acid is preferably 9:1.
The present invention is not particularly limited the UPLC-MS/MS method detected, selects detection well known to those skilled in the art
Method.
In the present invention, the detection limit of the triazole bactericidal agent is preferably 4.82~11.97ng/mL, more preferably
5.50~10.50ng/mL, more preferably 6.50~7.50ng/mL.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
Sequentially added in 100mL pyrex bottle 0.2mmol triazolone, 0.6mmol methacrylic acid (MAA) and
50mL acetonitrile is uniformly mixed, the logical N of ultrasound at 25 DEG C210min is placed on self assembly 10h in 25 DEG C of constant temperature gas bath oscillators, then
25mg azodiisobutyronitrile (AIBN) and 3mmol ethylene glycol dimethacrylate (EGDMA) is added, is uniformly mixed, leads to
N210min is placed on 25 DEG C of thermostatic water bath vibrator prepolymerization 2h, temperature is then warming up to 40 DEG C with 0.5 DEG C/min, polymerization
18h.After polymerization, stands to room temperature and outwell supernatant then with supercentrifuge (revolving speed 10000rpm) isolating polymer
Liquid, be put into Soxhlet extractor after object to be polymerized is dry, use methanol: acetic acid=6:1 (V/V) is eluted as eluant, eluent repetitive cycling
Template molecule, until supernatant can't detect triazolone on UPLC.Again with methanol solution washing copolymer, until polymerization
Object is in neutrality, and polymer is then put into 40 DEG C of vacuum ovens dryings to constant weight, it is micro- to obtain triazolone molecularly imprinted polymer
Ball (MIPs).
As control, other than being added without template molecule, all steps are consistent with preparing for embodiment 1, obtain non-molecule
Imprinted polymer microballoon (NIPs).
The resulting MIPs and NIPs 20mg of embodiment 1 is accurately weighed in 10mL centrifuge tube, being separately added into 5mL concentration is
Triazolone-acetonitrile solution of 20mg/L.Staticadsorption experiment is carried out at 25 DEG C, and supernatant is taken to carry out UPLC inspection after the completion of absorption
It surveys, it is as shown in table 1 that adsorption performance data is calculated:
The absorption property result of the imprinting factor of MIPs in 1 embodiment 1 of table
As shown in Table 1, the imprinting factor of triazolone molecularly imprinted polymer MIPs obtained in embodiment 1 is 2.413.
Fig. 1 is the electron-microscope scanning figure of MIPs obtained in embodiment 1；
Fig. 2 is the particle size distribution figure of MIPs obtained in embodiment 1；
As Fig. 1 and Fig. 2 it is found that the partial size of MIPs obtained in embodiment 1 is between 206nm~215nm, and it is distributed single
One.
Fig. 3 is the Static Adsorption curve of MIPs obtained in embodiment 1；The combination Q of MIPs is with triazolone as shown in Figure 3
The increase of concentration and increase.QMIPsIt is consistently higher than QNIPs, this is because MIPs has specific adsorption site, both there is chemistry and inhaled
It is attached and there are physical absorptions, and NIPs only has physical adsorption way, so MIPs has stronger adsorption capacity compared to NIPs.
Fig. 4 is spy of the MIPs and NIPs obtained in embodiment 1 to 9 kinds of triazole bactericidal agents and 2 kinds of non-triazole pesticides
Opposite sex absorption figure；Fig. 4 shows that the polymer microballoon has good specific adsorption to most of triazole bactericidal agents.
Embodiment 2
Using MIPs obtained in embodiment 1 as solid phase extraction filler, be applied to triazolone in mark-on tobacco leaf, nitrile bacterium azoles,
Tebuconazole, hexaconazole, olefin conversion, propiconazole, tricyclazole, glyoxalin and the detection of the Flusilazole rate of recovery.Detailed process are as follows:
1) 40 meshes are crossed after tobacco leaf control sample high-speed multifunctional being crushed crusher machine 1min, are then transferred to 50 DEG C of constant temperature
It dries in vacuum oven to constant weight.The above-mentioned dry tobacco sample of several pieces 1g is weighed, is respectively placed in 10mL centrifuge tube, is added
The residual mixed standard solution 1mL of 9 kinds of triazole bactericidal agent agricultures of various concentration, spiked levels are respectively 0.01,0.05,0.1,0.5 μ
G/g, then vortex oscillation 5min mixes well it, and 50 DEG C of vacuum drying 2h are put into after being stored at room temperature overnight to get mark-on is arrived
Tobacco sample.
2) 10mL acetonitrile solution is added into mark-on tobacco sample, supernatant is taken out in centrifugation after ultrasonic extraction 30min at 30 DEG C
Liquid crosses 0.22 μm of filter membrane, filtrate is transferred in 50mL rotary evaporation bottle, wait rotate.Then by filter residue and the cigarette of centrifugation bottom of the tube
Leaf extract remainder merges, and adds 5mL acetonitrile and carries out second of extraction (extraction conditions is with for the first time).Merge extract liquor twice, rotation
Turn after being evaporated to dryness, is redissolved, be finally fitted into brown liquid chromatogram sample injection bottle with 1mL acetonitrile, it is to be detected.
3) filling of molecularly imprinted solid phase extraction column: accurately weighing the MIPs and NIPs of several pieces 100mg, and it is solid to be packed into 3mL
(upper and lower ends place 0.45 μm of sieve plate) compacting is spare in phase extraction column, i.e., is prepared into MISPE column respectively
(Molecularly Imprinted SolidPhase Extraction, MISPE) and NISPE column (Noimprinted
SolidPhase Extraction,NISPE)。
4) 5mL methanol is added in extraction equipment and carries out pre-activate, then using 10mL acetonitrile as loading front activating；Using
The acetonitrile prepared in step 2) redissolves sample loading；Using methanol: the solution 2mL of ultrapure water=8:1 (V/V) is eluted；Most
Use methanol afterwards: the solution of acetic acid=9:1 (V/V) is eluted.Eluent is moved into 25mL eggplant-shape bottle, rotation is used after being evaporated
1mL acetonitrile solution redissolves, upper UPLC-MS/MS detection.
The rate of recovery the results are shown in Table 2, it can be found that in addition to Flusilazole, other 8 kinds of triazole bactericidal agents are in spiked levels
Average recovery rate within the scope of 0.01~0.5 μ g/g is 70.14~105.43% (n=6), and the standard deviation repeatedly measured is
0.26~2.27%.Illustrate that this method favorable reproducibility, precision are high.In addition, using this micro- with triazolone molecular engram nanometer
Ball is that the Solid Phase Extraction combination UPLC-MS/MS detection method of adsorbent carries out the residual content of 8 kinds of triazole bactericidal agent agricultures in tobacco leaf
When detection, linear relationship is good (r >=0.9995) in a certain range.Method detection is limited to 4.82~11.97ng/mL, fixed
Amount limit (LOQ) is 16.07~39.90ng/mL.The trace detection residual to triazole type agricultures a variety of in tobacco leaf is realized, the results are shown in Table
3。
2 recovery of standard addition of table and precision (n=6)
Standard curve, the range of linearity, related coefficient, detection line and the quantitative limit of 3 eight kinds of triazole bactericidal agents of table
Embodiment 3
0.2mmol nitrile bacterium azoles, 0.6mmol MAA and 55mL acetonitrile are sequentially added in 100mL pyrex bottle, are mixed
Uniformly, the logical N of ultrasound at 30 DEG C210min is placed on self assembly 12h in 30 DEG C of constant temperature gas bath oscillators, and 30mg azo is then added
Bis-isobutyronitrile (AIBN) and 3mmol ethyleneglycol dimethacrylate (EGDMA) are uniformly mixed, and lead to N210min is placed on 30 DEG C of perseverances
Then tepidarium oscillator prepolymerization 3h is warming up to 55 DEG C with the rate of 1.2 DEG C/min, polymerize 20h.After polymerization, stand
Supernatant is outwelled, is put after object to be polymerized is dry then with supercentrifuge (revolving speed 10000rpm) isolating polymer to room temperature
Enter in Soxhlet extractor, use methanol: acetic acid=8:1 (V/V) is as eluant, eluent repetitive cycling eluted template molecule, until supernatant
Until can't detect triazolone on UPLC.Again with methanol solution washing copolymer, until polymer is in neutrality, it then will polymerization
Object is put into 40 DEG C of vacuum ovens dryings to constant weight, obtains triazolone molecular blotting polymer microsphere MIPs.
As control, other than being added without template molecule, all steps are consistent with preparing for embodiment 1, obtain non-molecule
Imprinted polymer NIPs.
The MIPs that embodiment 2 obtains is accurately weighed, in 10mL centrifuge tube, be separately added into 5mL concentration is NIPs 20mg
Triazolone-acetonitrile solution of 20mg/L.Staticadsorption experiment is carried out at 25 DEG C, and supernatant is taken to carry out UPLC inspection after the completion of absorption
It surveys, it is as shown in table 4 that adsorption performance data is calculated:
The imprinting factor for the MIPs that 4 embodiment 2 of table obtains
As shown in Table 4, the imprinting factor for the MIPs that embodiment 3 obtains is 2.386.
Fig. 5 is the particle size distribution figure of MIPs obtained in embodiment 3.Polyalcohol microspherulite diameter concentrates on as shown in Figure 5
210nm~220nm.
Embodiment 4
0.2mmol triazolone, 0.8mmol MAA and 50mL acetonitrile are sequentially added in 100mL pyrex bottle, are mixed
Uniformly, the logical N of ultrasound at 30 DEG C210min is placed on self assembly 12h in 30 DEG C of constant temperature gas bath oscillators, and 30mg azo is then added
Bis-isobutyronitrile AIBN and 2.4mmol diol dimethacrylate EGDMA is uniformly mixed, and leads to N210min is placed on 30 DEG C of constant temperature
Then temperature is slowly increased to 60 DEG C by water-bath oscillator prepolymerization 4h, polymerization is for 24 hours.After polymerization, standing to room temperature, then
With supercentrifuge (revolving speed 15000rpm) isolating polymer, supernatant is outwelled, is put into Soxhlet extraction after object to be polymerized is dry
In device, use methanol: acetic acid=9:1 (V/V) is as eluant, eluent repetitive cycling eluted template molecule, until supernatant is examined on UPLC
Until not detecting triazolone.Then polymer is put into 50 DEG C until polymer is in neutrality by again with methanol solution washing copolymer
Vacuum oven is dry to constant weight, obtains triazolone molecularly imprinted polymer MIPs.
As control, other than being added without template molecule, all steps are consistent with preparing for embodiment 1, obtain non-molecule
Imprinted polymer NIPs.
MIPs and NIPs 20mg obtained in embodiment 3 is accurately weighed in 10mL centrifuge tube, is separately added into 5mL concentration
For triazolone-acetonitrile solution of 20mg/L.Staticadsorption experiment is carried out at 25 DEG C, and supernatant is taken to carry out UPLC inspection after the completion of absorption
It surveys, it is as shown in table 5 that adsorption performance data is calculated:
The imprinting factor for the MIPs that 5 embodiment 5 of table obtains
As shown in Table 5, the imprinting factor for the MIPs that embodiment 4 obtains is 2.412.
Fig. 6 is the particle size distribution figure of MIPs obtained in embodiment 4.(polyalcohol microspherulite diameter concentrates on as shown in Figure 6
202nm~210nm.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (12)
1. a kind of preparation method of triazole type molecular blotting polymer microsphere, comprising the following steps:
1) it is carried out after ultrasound under oxygen-free environment from group after mixing triazole class compounds template molecule, function monomer and pore-foaming agent
Dress, obtains self assembly mixed liquor；
2) pre-polymerization is carried out after mixing the self assembly mixed liquor that step 1) obtains with acrylic ester cross-linking agent, azo-initiator
It closes, obtains prepolymerization liquid；The prepolymerized temperature is 20~40 DEG C；
3) polymerization reaction is being carried out after the prepolymerization liquid heating obtained step 2), is obtaining polymer；The speed of the heating
Rate is 0.5~1.2 DEG C/min, and the temperature of the polymerization reaction is 35~60 DEG C；
4) the triazole class compounds template molecule elution in the polymer for obtaining step 3) obtains the polymerization of triazole type molecular engram
Object microballoon；
It is carried out under the conditions of the polymerization reaction earthquake in prepolymerization and the step 2) in the step 1).
2. preparation method according to claim 1, which is characterized in that triazole class compounds template molecule in the step 1)
For triazolone, nitrile bacterium azoles, Tebuconazole, hexaconazole, olefin conversion, propiconazole, tricyclazole, glyoxalin or Flusilazole.
3. preparation method according to claim 1, which is characterized in that function monomer is acrylic acid, α-in the step 1)
Methacrylic acid, trifluoromethyl acrylate or acrylamide.
4. preparation method according to claim 1, which is characterized in that pore-foaming agent is chloroform, toluene, second in the step 1)
Nitrile or methylene chloride.
5. preparation method described in any one according to claim 1~4, which is characterized in that triazole type in the step 1)
The amount ratio for closing object template molecule, function monomer and pore-foaming agent is 1mol:2~6mol:30~60ml.
6. preparation method according to claim 1, which is characterized in that the temperature of self assembly is 4~30 in the step 1)
DEG C, the time of the self assembly is 2~12h.
7. preparation method according to claim 1, which is characterized in that acrylic ester cross-linking agent is second in the step 2)
Diol dimethacrylate or trimethylol-propane trimethacrylate.
8. preparation method according to claim 1, which is characterized in that azo-initiator is azo two in the step 2)
Isobutyronitrile or azobisisoheptonitrile.
9. according to claim 1, preparation method described in 7 or 8, which is characterized in that esters of acrylic acid is crosslinked in the step 2)
The mass ratio of agent, azo-initiator and triazole class compounds template molecule is 4~20:1:1.
10. preparation method according to claim 1, which is characterized in that the concussion in the step 2) and the step 3)
Condition is provided by constant temperature oscillator, and the revolving speed of the isothermal vibration device is 50~150rpm.
11. the triazole type molecular blotting polymer microsphere that method described in claim 1~10 any one is prepared, described
The particle size range of polymer microballoon is 190~220nm, and the size distribution of the polymer microballoon is single, average grain diameter 198nm
~203nm.
12. triazole type molecular blotting polymer microsphere described in claim 11 is in the residual trace detection of triazole bactericidal agent agriculture
Using.
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